KR100807454B1 - Aromatic carboxylic acids, acid halides thereof and processes for preparing both - Google Patents

Abstract

A novel aromatic carboxylic acid, an acid halide derivative thereof and a method for producing the same, which are useful as a raw material for a high molecular compound, particularly a condensed polymer compound having excellent heat resistance, are disclosed.

The aromatic carboxylic acid and acid halide derivatives thereof of the present invention are represented by general formulas (1) and (2), respectively.

[A is -C ≡CR ¹ or

(Wherein R ¹ is a hydrogen atom, an alkyl group or an aromatic group, R ² is an alkyl group or an aromatic group), and X represents a halogen atom.]

It has a structure represented by. According to the present invention, these compounds can be produced with excellent efficiency by carrying out specific processes using isophthalic acid dialkyl ester derivatives and acetylene derivatives.

Description

Aromatic carboxylic acid, acid halide derivative thereof and preparation method thereof {AROMATIC CARBOXYLIC ACIDS, ACID HALIDES THEREOF AND PROCESSES FOR PREPARING BOTH}

The present invention relates to aromatic carboxylic acids, acid halide derivatives thereof and methods for their preparation. More specifically, the present invention relates to aromatic carboxylic acids and acid halide derivatives thereof useful as raw materials for high molecular compounds, particularly condensed polymer compounds having excellent heat resistance, and the like, as well as methods for efficiently preparing the same.

Aromatic carboxylic acids having two carboxyl groups and acid halides thereof in one molecule are used as raw materials for aromatic polyamide resins, polyallylate resins, polybenzoxazole resins, polybenzothiazole resins, and the like. Accordingly, resins having various structures are manufactured and used.

On the other hand, these resins are generally thermoplastic polymer compounds, but have excellent heat resistance and are widely used for high temperature applications. As a result, attempts have been made to introduce thermosetting substituents as a means to improve heat resistance, and thus raw materials used in such methods have been desired.

In view of these circumstances, the first object of the present invention is to provide aromatic carboxylic acids and derivatives thereof useful as raw materials for polymer compounds, especially condensed polymer compounds having excellent heat resistance, and the second object is to produce them with excellent efficiency. will be.

The present inventors have conducted research to achieve the above-mentioned object, and as a result, the first object can be achieved by the aromatic carboxylic acid and the acid halide derivative thereof having a specific structure, and these have excellent efficiency by performing a specific process. It has been found that the present invention can be prepared in the above, and the second object can be achieved. This invention is completed based on such knowledge.

That is, the present invention,

(1) General formula (1)

[Wherein A is the following equation

-C ≡CR ¹ ... (a)

or

Wherein R ¹ represents a hydrogen atom, an alkyl group or an aromatic group, and R ² represents an alkyl group or an aromatic group.

Aromatic carboxylic acid, characterized by having a structure represented by

(2) General formula (2)

[Wherein A is the following equation

-C ≡CR ¹ ... (a)

or

(Wherein R ¹ is a hydrogen atom, an alkyl group or an aromatic group, R ² is an alkyl group or an aromatic group), and X represents a halogen atom.]

Acid halide derivatives of aromatic carboxylic acids, having a structure represented by

(3) General formula (3)

[Wherein D represents a leaving group and R represents a lower alkyl group]

Compound represented by and general formula (4)                 

HC ≡C-E ... (4)

[Wherein E represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group or an aromatic group.]

Reacting the compound represented by the following general formula (5),

[Wherein R and E have the same meanings as above]

After the compound represented by the above formula was produced and treated in the presence of an alkali metal hydroxide, the general formula (6)

[Wherein R ¹ represents a hydrogen atom, an alkyl group or an aromatic group, and M represents an alkali metal.] A compound represented by the following formula is produced, followed by acid treatment.

[Wherein, R ¹ is as defined above.]

Method for producing an aromatic carboxylic acid represented by

(4) General formula (7)

[Wherein D represents a leaving group and R represents a lower alkyl group]

Compound represented by general formula (8)

HC ≡CR ² ... (8)

[Wherein, R ² represents an alkyl group or an aromatic group.]

By reacting the compound represented by the formula (9)

[Wherein R and R ² are the same as defined above.]

After obtaining the compound represented by the general formula (10) by treating in the presence of an alkali metal hydroxide

[Wherein M represents an alkali metal and R ² is as defined above.]

General formula (1-2), characterized in that the compound represented by

[Wherein, R ² is as defined above.]

Method for producing an aromatic carboxylic acid represented by

(5) General formula (1-1)

[Wherein, R ¹ represents a hydrogen atom, an alkyl group or an aromatic group.]

Compound represented by or General formula (6)

[Wherein M represents an alkali metal and R ¹ is as defined above.]

Formula (2-1), characterized in that the compound represented by the treatment with a halogenating agent

[Wherein X represents a halogen atom and R ¹ is as defined above.]

A method for producing an acid halide derivative of an aromatic carboxylic acid represented by

(6) General formula (1-2)

[Wherein, R ² represents an alkyl group or an aromatic group.]

Compound represented by or General formula (10)

[Wherein M represents an alkali metal and R ² is as defined above.]

Formula (2-2), characterized in that the compound represented by the treatment with a halogenating agent

[Wherein X represents a halogen atom and R ² is as defined above.]

It is to provide a method for producing an acid halide derivative of an aromatic carboxylic acid represented by.

Best Mode for Carrying Out the Invention
The aromatic carboxylic acid and the acid halide derivative of the aromatic carboxylic acid of the present invention are represented by general formula (1) and general formula (2), respectively.

It is a novel compound which is not known in the literature until now with the structure represented by.

In the formulas (1) and (2), A is a formula

-C ≡CR ¹ ... (a)

or

[Wherein R ¹ is a hydrogen atom, an alkyl group or an aromatic group, and R ² is an alkyl group or an aromatic group.]

The group represented by is represented and X in General formula (2) represents a halogen atom.

That is, to the aromatic carboxylic acid represented by the said General formula (1), General formula (1-1)

[Wherein, R ¹ is as defined above.]

Aromatic carboxylic acid represented by general formula (1-2)

[Wherein, R ² is as defined above.]

There is an aromatic carboxylic acid represented by the above, and the acid halide derivatives of the aromatic carboxylic acid represented by the above general formula (2) include general formula (2-1)

[Wherein, R ¹ is as defined above.]

Acid halide derivatives of the aromatic carboxylic acid represented by the general formula (2-2)

[Wherein R ² is as defined above]

There is an acid halide derivative of an aromatic carboxylic acid represented by.

In the acid halide derivatives of the aromatic carboxylic acids represented by the general formulas (2-1) and (2-2) above, an acid chloride derivative whose X is a chlorine atom is preferable in view of practical use.

The general formula (1) and in the formula (2), R ¹ a phenyl group with an ethyl group, a propyl group, a butyl group such as an alkyl group and an aromatic group, an alkyl group and aromatic group represented by R ² in are an alkyl group, an aromatic group, a naphthyl And a methyl group, anthryl group, quinolyl group, and quinoxalyl group.

The following describes the preparation of such compounds.                 

First, the acid halide derivatives of the aromatic carboxylic acid represented by the general formula (1-1) and the aromatic carboxylic acid represented by the general formula (2-1) can be produced by the following routes.

In formula (3), D is a leaving group, in formulas (3) and (5), R is a lower alkyl group, preferably methyl group, and in formulas (4) and (5), E is trimethyl silyl In the formula (6), M represents an alkali metal, and in formulas (6), (1-1) and (2-1), R ¹ represents a hydrogen atom. In the general formula (2-1), X represents a halogen atom, preferably a chlorine atom.

First, as starting materials, a dialkyl ester compound of isophthalic acid in which the fifth position on the benzene ring represented by the general formula (3) is substituted with the leaving group D and a compound in which one of the acetylenes are substituted with the E group [General formula (4)] By coupling reaction, the compound represented by General formula (5) can be obtained. It is preferable to use a catalyst as said coupling reaction, For example, transition metal catalysts, such as palladium, can be used. In the coupling reaction under this catalyst, a group which is easily separated from the aromatic ring is preferable, and halogen, trifluoromethane sulfonyloxy group such as fluorine, chlorine, bromine and iodine, and the like are preferable. The group which acts as a protecting group is preferable, In this case, a trimethyl silyl group, a hydroxy propyl group, etc. are selected, and Substituent E is an aromatic group, There may be mentioned an alkyl group, an aromatic group include a phenyl group, a naphthyl group, an anthryl group, quinolyl group, quinoxaline save group.

Next, the compound is subjected to dealkylation reaction from a carboxylic ester group using an alkali metal hydroxide, and in the compound represented by the general formula (5), when the E group is a protecting group, the deprotection treatment is performed simultaneously. The alkali metal salt of the isophthalic acid derivative represented by general formula (6) can be obtained.

Furthermore, by treating the alkali metal salt of the isophthalic acid derivative represented by the general formula (6) with an acid and treating the aromatic carboxyl represented by the general formula (1-1) with a halogenating agent, preferably a chlorinating agent, An acid halide derivative and preferably an acid chloride derivative represented by 2-1) can be obtained.

The isophthalic acid dialkyl ester in which the fifth position on the benzene ring represented by the general formula (3) is substituted with D is the following reaction formula when the leaving group D is a trifluoromethane sulfonyloxy group.

R is a lower alkyl group.

5-trifluoromethane sulfonyloxy isophthalic acid dialkyl ester by esterifying 5-hydroxy isophthalic acid dialkyl ester [formula (11)] with trifluoromethane sulfonic anhydride [formula (12)]. Formula (3-1) can be obtained.

In addition, the following reaction formula

Sandmeyer proceeding via a diazonium salt [formula (14)] using 5-amino isophthalic acid [formula (13)] as a raw material so as to be represented by [D ¹ is a halogen atom, R is a lower alkyl group]. By reacting, the isophthalic acid represented by Formula (15) in which the leaving group is halogen can be produced. Then, by alkyl esterifying carboxylic acid, the leaving group D is represented by Formula (3-2) in which halogen is represented. Isophthalic acid dialkyl ester can be obtained easily.

Hereinafter, the example of the manufacturing method of the acid halide derivative of aromatic carboxylic acid represented by the said General formula (1-1) and aromatic carboxylic acid represented by General formula (2-1) is demonstrated.

As an example using 5-bromo isophthalic acid dialkyl ester [D = Br] in formula (3), first, 5-bromo isophthalic acid dialkyl ester is brominated with 5-amino isophthalic acid (formula (13)]. By reacting hydrochloric acid and sodium nitrite, diazonium bromate [D ¹ = Br in formula (14) is obtained. Nitrogen gas is generated by reacting this with cuprous bromide, and 5-bromo isophthalic acid is used. 15), D ¹ = Br] can be obtained. Subsequently, lower alcohols and carboxylic acids are esterified by adding and refluxing lower alcohols in the presence of an acidic catalyst such as sulfuric acid in an inert gas atmosphere such as nitrogen, argon, and helium. By reaction to obtain 5-bromo isophthalic acid dialkyl ester [D ¹ = Br] in formula (3-2). The amount of lower alcohol is used in excess to shift the reaction equilibrium to the product side. In addition, in order to reduce the amount of water in the system, it is better to distill the lower alcohol in advance.

In addition, when 5-trifluoromethane sulfonyloxy isophthalic-acid dialkyl ester [in Formula (3), D = trifluoromethane sulfonyloxy group] is used, first 5-hydroxy isophthalic-acid dialkyl ester [ Formula (11)] and a base are dissolved in a solvent, trifluoromethane sulfonic anhydride [Formula (12)] is added to the solution cooled to about -78 degreeC-10 degreeC, and it is the temperature range of 0 degreeC-below the boiling point of a solvent. At this time, the reaction time is not particularly limited. The cooling is performed before the addition of trifluoromethane sulfonic anhydride in the above reaction because the reaction is exothermic, and the reaction proceeds rapidly at a temperature higher than this. This is because there is a risk of the solvent suddenly boiling.

The reaction product thus obtained can be subjected to usual separation means, for example, extraction, separation, concentration and the like, to obtain 5-trifluoromethane sulfonyloxy isophthalic acid dialkyl ester.

Moreover, this can be refine | purified by recrystallization, column chromatography, etc. as needed.

As a usage-amount of trifluoromethane sulfonic anhydride, 1-1.5 equivalent times is preferable with respect to 5-hydroxy isophthalic-acid dialkyl ester.

Preferred examples of the base include tertiary amines having no active hydrogen, and specific examples include pyridines such as pyridine and methylpyridine, trialkylamines such as triethylamine and tributylamine, and the like. It is preferable to use 1-1.5 equivalent times with respect to the total amount of 5-hydroxy isophthalic-acid dialkyl ester and trifluoromethane sulfonic anhydride.

Examples of the solvent include reactions of aromatic hydrocarbons such as benzene, toluene, n-hexane, cyclohexane, petroleum ether, ethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloromethane and chloroform, hydrocarbons, ethers and halogenated hydrocarbons. The inert solvent alone or a mixture thereof can be mentioned, and the amount of the inert solvent is not particularly limited.

In addition, the presence of water in the solvent causes an additional reaction with trifluoromethane sulfonic anhydride, the reaction reagent, and the actual reaction equivalence ratio changes. Therefore, use an anhydrous solvent or determine the amount of water contained in advance to adjust the amount used. It is desirable to put more than equivalent amount.

Next, as a method of obtaining the compound represented by the general formula (5), the 5-bromo isophthalic acid dialkyl ester or 5-trifluoromethane sulfonyloxy isophthalic acid dialkyl ester obtained above is represented by the general formula (4). One side of acetylene

The reaction product can be obtained by coupling the compound substituted with the protecting group E, the alkyl group or the aromatic group E in the presence of a catalyst in an inert gas atmosphere such as nitrogen, argon or helium at a temperature range of about 20 to 150 ° C. The reaction time is not particularly limited. The reaction product obtained in this way can be subjected to separation operations such as concentration and reprecipitation to obtain the compound represented by the general formula (5). It can be refined by recrystallization.

The compound in which one side of the acetylene represented by the general formula (4) is protected by the protecting group E is not particularly limited as long as the protecting group E is a compound which can be deprotected by the hydroxide of an alkali metal, but the protecting group E is trimethylsilyl acetylene or a hydride group 3-Methyl-1-butyn-3-ol, which is a hydroxypropyl group, is very suitable. The compound represented by the general formula (4) is sufficient to calculate the equivalent of 1 equivalent by weight to the compound represented by the general formula (3). In order to proceed completely, the addition amount may be adjusted in the range of 1 to 2 equivalent times.

As the catalyst system, any catalyst system capable of forming a carbon-carbon bond can be used without particular limitation, but it is preferable to use a catalyst system composed of dichlorobis (triphenylphosphine) palladium, copper iodide and triphenylphosphine. Although the addition amount of (triphenylphosphine) palladium is not specifically defined, 0.1-1 mol% with respect to the compound represented by General formula (5), Triphenyl phosphine is 1-20 with respect to dichloro bis (triphenylphosphine) palladium. Equivalent pear, copper iodide is preferably in the range of 1 to 5 equivalents.

As the solvent used in this reaction, an amine solvent is preferably used to capture the generated acid and promote the catalytic reaction. Such solvents include tertiary amines such as diethylamine, triethylamine, butylamine and tributylamine, and cyclic amines such as pyridine and piperidine. These solvents may be used alone or in combination of two or more thereof. Although the amount of use thereof is not particularly limited, it is preferably 2 to 50 times by weight based on the raw materials. In addition, it is preferable to distill these solvents in advance to prevent side reactions and loss of catalytic activity.

 Next, as a method of obtaining an alkali metal salt of an isophthalic acid derivative represented by the general formula (6), the compound represented by the general formula (5) is treated in the presence of an alkali metal hydroxide in a solvent to dealkylate the carboxylic ester group. And in the compound represented by the general formula (5), in the case where the E group is a protecting group such as trimethylsilyl group, hydroxypropyl group or the like, deprotection of the ethynyl group is also performed simultaneously to obtain a reaction product. And the reaction time is not particularly limited, but the reaction temperature is preferably in the range of room temperature to the reflux temperature of the solvent. The obtained crystals are cooled to separate the precipitated crystals, and alcohols such as methanol, ethanol, butanol and isopropanol are used. By washing with a solvent and then drying, an alkali metal salt of isophthalic acid derivative represented by the general formula (6) can be obtained. have.

As alkali metal hydroxide, potassium hydroxide and sodium hydroxide are preferable, and addition amount is 3 or more times more preferable with respect to the compound represented by General formula (5).

The reaction solvent is not particularly limited except for esters reacting with the alkali metal hydroxide, but alcohol solvents such as methanol, ethanol, butanol, and isopropanol, which have high solubility of the alkali metal hydroxide, are preferable. The amount of the solvent is not particularly limited. Considering the problem of operability, the range of 5 to 50 times by weight with respect to the compound represented by the general formula (5) is good.

The aromatic carboxylic acid represented by the general formula (1-1) of the present invention dissolves the alkali metal salt [formula (6)] of the isophthalic acid derivative obtained above in water, and is preferably an acid such as hydrochloric acid, sulfuric acid or nitric acid. The precipitate is obtained by acidification to pH1, which can be taken, washed and dried. In this case, if left for a long time under strong acidity, the ethynyl moiety may receive side reactions such as addition reaction or polymerization, and therefore it is preferable to treat it for a short time. ．

The acid halide derivatives of the carboxylic acid represented by the general formula (2-1) of the present invention may be obtained by using the alkali metal salt [formula (6)] of the isophthalic acid derivative obtained above in a solvent or an excess of a halogenating agent as a solvent. It can be obtained by reacting with a halogenating agent at a temperature in the range of about 0 to 70 ° C., then removing the solvent, washing the obtained solid with a solvent, and subsequently recrystallizing. In addition, isophthalic acid represented by the general formula (6) is obtained. Instead of the alkali metal salt of the derivative, an aromatic carboxylic acid represented by the general formula (1-1) may be used.

As the halogenating agent, thionyl halide, oxalyl halide and the like are preferable, and the amount of the halogenating agent is usually 2 equivalents or more to the alkali metal salt of the isophthalic acid derivative represented by the general formula (6), and there is no particular upper limit. When the solvent is not used, it may be used in excess of 10 equivalents or more.

The solvent is not particularly limited, but for example, aromatic hydrocarbons such as benzene, toluene and xylene, hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene Halogenated hydrocarbons, and the like. These may be used as arbitrary amounts with respect to the alkali metal salt of the isophthalic acid derivative represented by the general formula (6).

At this time, in order to accelerate the reaction, a base such as N, N-dimethyl formamide or pyridine may be added.

Moreover, you may add polymerization inhibitors, such as hydroquinone and a hydroquinone monomethyl ether, in order to suppress superposition | polymerization in an ethynyl site | part.

Furthermore, the aromatic carboxylic acid represented by the general formula (1-1) obtained by acid treatment of the alkali metal salt of the isophthalic acid derivative represented by the general formula (6) is treated with a halogenating agent and represented by the general formula (2-1). An acid halide derivative can be obtained. As the halogenating agent, a chlorinating agent is preferable from the practical point of view.

Next, the acid halide derivatives of the aromatic carboxylic acid represented by the general formula (1-2) and the aromatic carboxylic acid represented by the general formula (2-2) can be produced by the following routes.

In general formula (7), D is a leaving group, and in general formula (8), (9), (10), (1-2) and (2-2), R <^2> is an alkyl group or an aromatic group, In (10), M represents an alkali metal, in formula (2-2), X represents a halogen atom, preferably a chlorine atom, and in each formula, R represents a lower alkyl group and preferably a methyl group.

First, as a starting material, an ether bond formation reaction using a hydroxy isophthalic acid dialkyl ester represented by the formula (11) and a fluoro nitrobenzene represented by the formula (16) and a base such as potassium carbonate or sodium carbonate is used. 5- (nitrophenoxy) isophthalic acid dialkyl ester represented by (17) can be obtained.

The compound is treated with palladium-activated carbon or platinum-activated carbon in a hydrogen atmosphere or with tin or tin chloride under acidic conditions to obtain 5- (aminophenoxy) isophthalic acid dialkyl ester represented by formula (18).

This compound is diazotized by adding sodium nitrite in an acidic solution, and is added to potassium iodide, sodium iodide, copper bromide or copper chloride to give a compound represented by the general formula (7). Iophenphenoxy) isophthalic acid dialkyl ester, 5- (bromophenoxy) isophthalic acid dialkyl ester, or 5- (chlorophenoxy) isophthalic acid dialkyl ester can be obtained.

As another method, 5- (hydroxyphenoxy) isophthalic acid dialkyl ester of the compound represented by formula (19) can be obtained by diazotizing the compound represented by formula (18) with sodium nitrite and heating under acidic conditions. By esterifying this compound with trifluoromethane sulfonic anhydride, 5- (trifluoromethane sulfonyloxyphenoxy in which the leaving group D is a trifluoromethane sulfonyloxy group in the compound represented by the general formula (7). Isophthalic acid dialkyl ester can be obtained.

delete

In the same manner as described above, one of the dialkyl ester compound represented by the general formula (7) and the acetylene represented by the general formula (8) is reacted with a compound substituted with a R ² group to represent the general formula (9). In addition, the substituent R ² includes an aromatic group or an alkyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthryl group, a quinolyl group, a quinoxalyl group, and an alkyl group as an alkyl group. A propyl group, a butyl group, etc. are mentioned.

This compound is then dealkylated from a carboxylic ester group using an alkali metal hydroxide to obtain an alkali metal salt of an isophthalic acid derivative represented by the general formula (10).

In addition, the acid treatment of the alkali metal salt of the isophthalic acid derivative represented by the general formula (10) to the aromatic carboxylic acid represented by the general formula (1-2) with a halogenating agent, preferably a chlorinating agent, The halide derivative represented by 2-2), preferably an acid chloride derivative, can be obtained.

Hereinafter, the example of the manufacturing method of the acid halide derivative of aromatic carboxylic acid represented by the said General formula (1-2) and aromatic carboxylic acid represented by General formula (2-2) is demonstrated.

In the above production example, the 5- (nitrophenoxy) isophthalic acid dialkyl ester represented by the formula (17) is a 5-hydroxy isophthalic acid dialkyl ester [formula (11)] and fluoronitrobenzene [formula (16) ), 100 ° C. in the presence of a base such as potassium carbonate or sodium carbonate in a polar solvent such as N, N-dimethyl formamide, N, N-dimethyl acetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. The reaction time is not particularly limited. The amount of the solvent is not particularly limited. The amount of the base is used in 5-hydroxy isophthalic acid dialkyl ester. 1-10 equivalent times is preferable.

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In addition, 5- (aminophenoxy) isophthalic acid dialkyl ester represented by Formula (18) is a 5- (nitrophenoxy) isophthalic acid dialkyl ester [formula (17)] tetrahydrofuran, tetrahydrofuran / ethanol It is obtained by treating with a catalyst such as palladium-activated carbon or platinum-activated carbon in a hydrogen atmosphere, in a mixed solvent such as methanol or a solvent such as N, N-dimethyl formamide. At this time, the reaction time and the amount of the solvent are particularly The amount of the catalyst used is preferably 0.1 to 10 mol% relative to 5- (aminophenoxy) isophthalic acid dialkyl ester.

Alternatively, 5- (nitrophenoxy) isophthalic acid dialkyl ester may be treated with tin or tin chloride or the like under acidic conditions to obtain 5- (aminophenoxy) isophthalic acid dialkyl ester.

In the compound represented by the general formula (7), examples of the 5- (iodinephenoxy) isophthalic acid dialkyl ester in which the leaving group D is iodine include, first, 5- (iodinephenoxy) isophthalic acid dialkyl ester Aminophenoxy) isophthalic acid dialkyl ester [formula (18)] reacts with an aqueous solution of mineral acid and sodium nitrite to obtain a diazonium mineral acid salt, which is then reacted with potassium iodide or sodium iodide to generate nitrogen gas. The isophthalic acid dialkyl ester can be obtained. Examples of the mine include sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, and the like, and the amount thereof is not particularly limited. The amount of sodium nitrite and potassium iodide or sodium iodide is 5 It is preferably 1 to 2 equivalents based on-(aminophenoxy) isophthalic acid dialkyl ester.

In the compound represented by the general formula (7), examples of 5- (bromophenoxy) isophthalic acid dialkyl ester and 5- (chlorophenoxy) isophthalic acid dialkyl ester in which leaving group D is bromine and chlorine are mentioned in the above reaction. In the example, it can obtain by using copper bromide and copper chloride instead of potassium iodide or sodium iodide, respectively.

Further, examples of the 5- (trifluoromethane sulfonyloxyphenoxy) isophthalic acid dialkyl ester in which the leaving group D is a trifluoromethane sulfonyloxy group include, firstly, 5- (aminophenoxy) isophthalic acid dialkyl ester [ The diazonium mine salt is obtained by reacting photoacid and sodium nitrite, and this is heated under acidic conditions to obtain 5- (hydroxyphenoxy) isophthalic acid dialkyl ester [formula (19)].

Examples of the mine include sulfuric acid, hydrochloric acid, nitric acid, and the like. The amount thereof is not limited. The amount of sodium nitrite is preferably 1 to 2 equivalents based on 5- (aminophenoxy) isophthalic acid dialkyl ester.

Subsequently, 5- (hydroxyphenoxy) isophthalic acid dialkyl ester [formula (19)] and a base were dissolved in a solvent, trifluoromethane sulfonic anhydride was added to a solution cooled to about -78 ° C to 10 ° C. It is made to react in the temperature range of 0 degreeC-below the boiling point of a solvent. The reaction product obtained in this way is subjected to normal separation means, for example, extraction, separation, concentration, and the like, to give 5- (trifluoromethane sulfonyl Oxyphenoxy) isophthalic acid dialkyl ester can be obtained.

Moreover, this can be refine | purified by recrystallization, column chromatography, etc. as needed.

As a usage-amount of the said trifluoromethane sulfonic anhydride, 1-1.5 equivalent times with respect to 5- (hydroxyphenoxy) isophthalic-acid dialkyl ester is preferable.

As the base, an amine having no active hydrogen as a tertiary amine is preferable, and specific examples thereof include pyridines such as pyridine and methylpyridine, trialkylamines such as triethylamine and tributylamine, and the like. The amount used is preferably in the range of 1 to 1.5 equivalent times the total amount of 5- (hydroxyphenoxy) isophthalic acid dialkyl ester and trifluoromethane sulfonic anhydride.

Examples of the solvent include reactions of aromatic hydrocarbons such as benzene, toluene, n-hexane, cyclohexane, petroleum ether, ethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloromethane and chloroform, hydrocarbons, ethers, and halogenated hydrocarbons. A solvent alone or a mixture thereof may be mentioned, and the amount thereof is not particularly limited.

Next, as a method of obtaining the compound represented by General formula (9), the 5- (iodine phenoxy) isophthalic acid dialkyl ester or 5- (trifluoromethane sulfonyloxy phenoxy) isophthalic acid dialkyl ester obtained above is obtained. And a compound in which one of acetylene represented by formula (8) is substituted with an alkyl group or aromatic group R ² can be obtained by carrying out a coupling reaction in the same manner as the compound represented by formula (5).

Examples of the compound represented by the general formula (8) include ethynylbenzene, ethynyl naphthalene, ethynyl anthracene, ethynyl quinoline, ethynyl quinoxaline, 1-butyne, 1-pentine, 3,3-dimethyl-1 -Butyne, 1-hexyne, etc. are used, The usage-amount is 1-1.5 equivalent times with respect to the compound represented by General formula (7).

Next, as a method of obtaining the alkali metal salt of the isophthalic acid derivative represented by the general formula (10), dealkylation of the compound represented by the general formula (9) is carried out in the same manner as the compound represented by the general formula (6). You can get it by running

Here, as an addition amount of an alkali metal hydroxide, it is normally 2 equivalent times or more with respect to the compound represented by General formula (9).

The aromatic carboxylic acid represented by the general formula (1-2) is the same as the aromatic carboxylic acid represented by the above general formula (1-1) from the alkali metal salt of the isophthalic acid derivative represented by the general formula (10) obtained above. The acid halide derivative of the carboxylic acid represented by the general formula (2-2) may be prepared by combining the alkali metal salt of the isophthalic acid derivative represented by the general formula (10). Similarly, it can obtain by making it react in a solvent or an excess amount of halogenating agents as a solvent. In addition, an aromatic carboxylic acid represented by the general formula (1-2) may be used instead of the alkali metal salt of the isophthalic acid derivative represented by the general formula (10). Do.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited in any way by these examples.

The obtained compound was subjected to melting point measurement, ¹ H-NMR, ¹³ C-NMR, and measurement of various spectra and elemental analysis for characterization. The measurement conditions for each characteristic were as follows.

Test Methods

(1) Melting | fusing point: It measured with the temperature increase rate of 10 degree-C / min using the Seiko electronic DSC-200 type differential scanning calorimeter (DSC).

(2) Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR, ¹³ C-NMR): Measured using JNM-GSX400 manufactured by Nippon Electronics Co., Ltd. ¹ H-NMR was measured at a resonance frequency of 400 MHz and ¹³ C-NMR at a resonance frequency of ¹⁰ MHz, respectively. Determination of 5-ethynyl isophthalic acid as a deuterated solvent, deuterated dimethyl sulfoxide DMSO-d ₆ , 5- (2 -Phenylethynyl) isophthalic acid is deuterated acetone (CD ₃ ) ₂ CO, 5-ethynyl isophthalic acid chloride, 5- (2-phenylethynyl) isophthalic acid chloride is a deuterated solvent, deuterated chloroform CDCl ₃ was used respectively.

(3) Infrared spectroscopic analysis (IR): It measured by KBr purification method using JIR-5500 type | mold by Nippon Electronics.

(4) Mass spectrometry (MS): It measured by field desorption (FD) method using JMS-700 type | mold by Japan Electronics.

(5) Elemental analysis: Carbon and hydrogen were measured by PERKIN ELMER 2400 type, and chlorine was measured by the Frasco combustion titration method.

(Example 1)

 [Preparation of 5-trifluoromethane sulfonyloxy isophthalate dimethyl from 5-hydroxyisophthalic acid dimethyl]

Into a 5-liter four-necked flask equipped with a thermometer, a cooling tube, a calcium chloride tube and a stirrer, 190.0 g (0.904 mol) of 5-hydroxy isophthalate, 3 liters of dehydrated toluene and 214.7 g (2.718 mol) of dehydrated pyridine were placed. The mixture was cooled to -30 DEG C while stirring. Here, 510.2 g (1.808 mol) of trifluoromethane anhydrous anhydrous acid was slowly added dropwise, taking care not to increase the temperature above -25 DEG C. In this case, until the dropping was completed. One hour was required. After the addition, the reaction temperature was raised to 0 deg. C for 1 hour, and the reaction temperature was raised to room temperature for 5 hours. The obtained reaction mixture was poured into 4 liters of ice water and separated into an aqueous layer and an organic layer. The aqueous layer was extracted twice with 500 ml of toluene and this was added to the preceding organic layer. The organic layer was washed twice with 3 L of water, dried over 100 g of anhydrous magnesium sulfate, filtered and anhydrous. 294.0 g of pale yellow solid 5-trifluoromethane sulfonyloxy isophthalate was obtained by removing magnesium sulfate, removing toluene by rotary evaporation (yield 95%). The crude product was recrystallized from hexane. White needle crystals were obtained and used for the next reaction.

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[Preparation of 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol from 5-trifluoromethane sulfonyloxy isophthalic acid dimethyl]

125 g (0.365 mol) of dimethyl 5-trifluoromethane sulfonyloxy isophthalate obtained above and 1.1 g of triphenylphosphine in a 1 liter four-necked flask equipped with a thermometer, a gym lotion tube, a nitrogen introduction tube, and a stirrer. 0.00419 mol), 0.275 g (0.00144 mol) of copper iodide, and 33.73 g (0.401 mol) of 3-methyl-1butyn-3-ol were added thereto, and nitrogen was flowed. 375 m1 of dehydrated triethylamine and 200 m1 of dehydrated pyridine were added thereto, followed by stirring. After nitrogen was continuously flowed for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was added quickly and heated to reflux for 1 hour in an oil bath. Thereafter, triethylamine and The pyridine was distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500m1 of water, and the solid precipitated therefrom was taken out and washed twice with 500ml of water, 500m1 of 5 mol / L hydrochloric acid and 500m1 of water, respectively. The solid was dried under reduced pressure at 50 ° C, and 98.8g of 4- (3 , 5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol (yield 98%).

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[Preparation of 5-ethynyl isophthalic acid dipotassium salt from 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol]

Into a 5-liter four-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 3 liters of n-butanol and 182 g (2.763 mol) of potassium hydroxide (85%) were dissolved in a heated reflux solution. 95 g (0.344 mole) of (3,5 bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol was added thereto, followed by heating to reflux for 30 minutes. This was cooled in an ice bath to precipitate crystals. The crystals were washed twice with 1 liter of ethanol and dried under reduced pressure at 60 DEG C to obtain 88.87 g of 5-potynyl isophthalic acid dipotassium salt (97%).

 [Preparation of 5-ethynyl isophthalic acid from 5-ethynyl isophthalic acid dipotassium salt]

Insoluble matter was removed by dissolving 5 g (0.019 mol) of 5-ethynyl isophthalic acid dipotassium salt in 20m1 of ion-exchanged water and filtering with a 5C filter paper. When 5 mol / L hydrochloric acid had a pH of 1 The precipitated solid was taken out and washed and filtered twice with ion-exchanged water twice. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 3.6 g of 5-ethynyl isophthalic acid (yield 99.5%). ).

[Preparation of 5-ethynyl isophthalic acid dichloride from 5-ethynyl isophthalic acid dipotassium salt]

Into a 2-liter four-necked flask equipped with a thermometer, a zigzag cooling tube, and a stirrer, 80 g (0.3 mol) of 5-ethynyl isophthalic acid dipotassium salt and 400 milliliters of chloroform were added and cooled to 0 deg. 391 g (4.5 mol) of thionyl chlorides were dripped at this at 5 degrees C or less over 1 hour. Then, 4 ml of dimethyl formamide and 4 g of hydroquinone were added, and it stirred at 45-50 degreeC for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 150m1 of chloroform. The filtrate and the washing liquid were combined and concentrated under reduced pressure at 40 ° C or below, and the obtained residue was extracted twice with 200 ml of diethyl ether. Ethyl ether was distilled off under reduced pressure to obtain a semi-solid crude product. This was washed with anhydrous n-hexane, and then recrystallized with diethyl ether to obtain 13 g of 5-ethynyl isophthaloyl dichloride (yield 19%).

The spectral data of the 5-ethynyl isophthalic acid and 5-ethynyl isophthalic acid dichloride obtained are shown as follows. These data support that the obtained compound is the target product.

[5-Ethynyl Isophthalic Acid (C ₁₀ H ₆ O ₄ )]

Appearance: white powder

Melting Point: 106.2 ° C (DSC, 10 ° C / min)

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 8.16 (s, 2H), 8.45 (s, 1H)

¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 81.5, 82.6, 122.7, 130.0, 131.9, 135.9, 165.7

IR (KBr, cm ^-1 ): 3272, 3081, 1797, 1741, 1438, 1265, 800, 761

MS (FD) (m / z): 190 (M ⁺ )

Elemental Analysis:

Theoretical C: 63.16% H: 3.18% O: 33.66%

Found C: 63.24% H: 3.09% O: 33.67%

[5-Ethynyl Isophthalic Acid Dichloride (C ₁₀ H ₄ O ₂ Cl ₂ )]

Appearance: white solid

Melting Point: 49 ℃ (DSC ， 10 ℃ / min)                 

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.47 (s, 2H), 8.77 (s, 1H)

¹³ C-NMR (100 MHz, CDCl ₃ ): δ 80.0, 81.6, 124.9, 133.0, 134.7, 139.8, 166.6

IR (KBr, cm ^-1 ): 3465, 3077, 1766, 1736, 1151, 1022, 802, 740

MS (FD) (m / z): 190 (M ⁺ -2Cl)

Elemental Analysis:

Theoretical C: 52.86% H: 1.77% C1: 31.21% O: 14.08%

Found C: 52.74% H: 1.70% C1: 30.89% O: 14.67%

(Example 2)

[Preparation of 1- (3,5-bis (methoxycarbonyl) phenyl) 2-phenylethine from 5-trifluoromethane sulfonyloxy isophthalic acid dimethyl]

125 g (0.365 mole) of dimethyl 5-trifluoromethane sulfonyloxyisophthalate obtained in the same manner as in Example 1 in a one-liter four-necked flask equipped with a thermometer, a gym lotion tube, a nitrogen inlet tube, and a stirrer; 1.1 g (0.00419 mol) of phosphine, 0.275 g (0.00144 mol) of copper iodide, 40.95 g (0.401 mol) of ethynylbenzene were added, and nitrogen was flowed. 375 ml of dehydrated triethylamine and 200 ml of dehydrated pyridine were added and stirred and dissolved. After continuously flowing nitrogen for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was added quickly, and the mixture was heated to reflux for 1 hour in an oil bath. Thereafter, triethylamine and pyridine were added. Distillation under reduced pressure gave a viscous brown solution. The precipitated solid was taken out in 500m1 of water, and washed twice with 500m1 of water, 500m1 of 5 mol / L hydrochloric acid and 500m1 of water, respectively. The solid was dried under reduced pressure at 50 ° C and 80.8g of 1- (3,5- Bis (methoxycarbonyl) phenyl) -2-phenylethine was obtained (yield 75%).

[Preparation of 5- (2-phenylethynyl) isophthalic acid dipotassium salt from (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethine]

In a 5-liter four-necked flask equipped with a thermometer, a cooling tube and a stirrer, 3 liters of n-butanol and 180 g (2.72 moles) of potassium hydroxide (85%) were dissolved under heating and refluxed. 80 g (0.272 mol) of 5-bis (methoxycarbonyl) phenyl) -2-phenylethine was added thereto, and the mixture was heated to reflux for 30 minutes. This was crystallized by cooling precipitated in an ice bath. The crystals were washed twice with 1 liter of ethanol and dried at 60 ° C. under reduced pressure to obtain 90.35 g of 5- (2-phenylethynyl) isophthalic acid dipotassium salt (97%).

[Production of 5- (2-phenylethynyl) isophthalic acid from 5- (2-phenylethynyl) isophthalic acid dipotassium salt]

6.5 g (0.019 mol) of 5- (2-phenylethynyl) ethynyl isophthalic acid dipotassium salt was dissolved in 20 ml of ion-exchanged water and filtered through a 5C filter paper to remove insoluble materials. 5 mol / L Hydrochloric acid was added with stirring until pH was 1. The precipitated solid was taken, washed with ion-exchanged water and filtered twice more. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 5- (2-phenyl). Etinyl) isophthalic acid 5.0g was obtained (yield 99.5%).

[Preparation of 5- (2-phenylethynyl) isophthalic acid dichloride from 5- (2-phenylethynyl) isophthalic acid dipotassium salt]

Into a 2-liter four-necked flask equipped with a thermometer, a zigzag cooling tube, and a stirrer, 82.1 g (0.24 mol) of dipotassium 5- (2-phenylethynyl) isophthalic acid salt and 400 liters of 1,2-dichloroethane were added to 0 ° C. 391 g (4.5 mol) of thionyl chloride was added dropwise over 1 hour at 5 DEG C or lower. Thereafter, 4 ml of dimethyl formamide and 4 g of hydroquinone were added, followed by stirring at 45 to 50 DEG C for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 150m1 of chloroform. The filtrate and washings were combined, concentrated under reduced pressure at 40 占 폚 or lower, and the obtained residue was extracted and filtered twice with 200m1 of diethyl ether. The diethyl ether was distilled off under reduced pressure from the semi-solid crude product. This was washed with anhydrous n-hexane, and then recrystallized with diethyl ether to obtain 13.8 g of 5- (2-phenylethynyl) isophthaloyl dichloride (yield 19%).

The spectral data of 5- (2-phenylethynyl) isophthalic acid and 5- (2-phenylethynyl) isophthalic acid dichloride obtained are shown below. These data support that the obtained compound is the target product.

[5- (2-phenylethynyl) isophthalic acid (C ₁₆ H ₁₀ O ₄ )]

Appearance: white powder

Melting Point: 99.7 ° C (DSC, 10 ° C / min)

¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO): δ 7.44 (m, 3H), 7.64 (m, 2H), 8.35 (d, 2H, J = 1.6 Hz), 8.63 (t, 1H, J = 1.6 Hz)

¹³ C-NMR (100 MHz, (CD ₃ ) ₂ CO): δ 88.0, 91.7, 123.2, 125.0, 129.5, 129.5, 129.9, 131.0, 132.5, 132.7, 132.7, 136.8, 166.2

IR (KBr, cm ^-1 ): 3549, 2968, 2365, 1722, 1492, 1446, 1276, 917, 756, 674

MS (FD) (m / z): 266 (M ⁺ )

Elemental Analysis:

Theoretical C: 72.18% H: 3.79% O: 24.04%

Found C: 70.86% H: 3.64% O: 25.50%

[5- (2-phenylethynyl) isophthalic acid dichloride (C ₁₆ H ₈ O ₂ Cl ₂ )]

Appearance: white solid

Melting Point: 124 ℃ (DSC ， 10 ℃ / min)

¹ H-NMR (400 MHz, CDC1 ₃ ): δ 7.40 (m, 3H), 7.57 (m, 2H), 8.50 (d, 2H, J = 1.6 Hz), 8.73 (t, 2H, J = 1.6 Hz)

¹³ C-NMR (100MHz, CDC1 ₃ ): δ85.7, 93.6, 121.6, 126.2, 128.6, 129.5, 131.9, 132.2, 134.6, 139.2, 166.8

IR (KBr, cm ^-1 ): 3489, 3075, 2216, 1756, 1580, 1489, 1440, 1329, 1218, 1145, 1000, 819, 690

MS (FD) (m / z): 266 (M ⁺ -2C1)

Elemental Analysis:

Theoretical C: 63.39% H: 2.66% C1: 23.39% O: 10.56%

Found C: 63.04% H: 2.49% Cl: 22.69% O: 11.78%

(Example 3)

[Production of 5-bromoisophthalic acid]

Into a one-liter four-necked flask equipped with a thermometer, agitator, and dropping lot, 99.18 g (0.55 mol) of 5-hydroxy isophthalic acid, 165 m1 of 48 wt% hydrobromic acid, and 150 m1 of distilled water were stirred. The flask was cooled to 5 ° C or lower. Then, what dissolved 39.4 g (0.57 mol) of sodium nitrite in 525 ml of distilled water was dripped here over 1 hour, and the diazonium salt aqueous solution was obtained. Into a 3-liter four-necked flask equipped with a thermometer, a gym lotion tube, a dropping lot, and a stirrer, 94.25 g (0.66 mol) of cuprous cup bromide and 45 ml of 48% by weight hydrobromic acid were added and stirred. The flask was cooled to 0 ° C. or lower, and the diazonium salt solution was added dropwise for 2 hours. After completion of the dropwise addition, the flask was stirred at room temperature for 30 minutes and then refluxed for 30 minutes. After cooling, the precipitate was taken out and washed twice with 2 L of distilled water. And the white solid obtained was dried under reduced pressure at 50 degreeC for 2 days, and 117 g of crude products were obtained. It was used for the next reaction without purification.

[Preparation of 5-bromo isophthalic acid dimethyl from 5-bromo isophthalic acid]

 110 g of 5-bromo isophthalic acid, 500 m1 of methanol and 10 g of concentrated sulfuric acid were added to a 500 m1 flask equipped with a stirrer and a chilled cooling tube, and refluxed for 6 hours. After cooling, the mixture was dropped into 1 L of distilled water and this was 5% by weight. The precipitate was taken out and washed twice with 2 L of distilled water, and the obtained white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 109 g (0.4 mol) of dimethyl 5-bromo isophthalate (yield 89%). ).

 [Preparation of 4- (3,5-bis (methoxy carbonyl) phenyl) -2-methyl-3-butyn-1-ol from 5-bromo isophthalic acid dimethyl]

In Example 1, 98.8 g was carried out similarly to Example 1 except having replaced 125 g (0.365 mol) of 5-dimethyl sulfonyloxy isophthalic acid dimethyls with 99.7 g (0.365 mol) of 5-bromo isophthalic-acids. 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol was obtained (yield 98%).

In the same manner as in Example 1, 5-ethynyl isophthalic acid dipotassium salt, 5-ethynyl isophthalic acid and 5-ethynyl isophthalic acid dichloride can be obtained. 5-ethynyl isophthalic acid and 5-ethynyl iso The appearance, melting point and spectral data of ¹ H-NMR, ¹³ C-NMR, IR, MS, and elemental analysis of the phthalic acid dichloride were all in agreement with Example 1 to show that the same compound was obtained.

(Example 4)

 [Preparation of 1- (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethine]

In Example 2, 125 g (0.365 mol) of 5-trifluoromethane sulfonyloxy isophthalic acid dimethyl was used in the same manner as in Example 3, except that 99.7 g (0.365 mol) of 5-bromo isophthalic acid dimethyl was obtained. In the same manner, 80.8 g of 1- (3,5-bis (methoxy carbonyl) phenyl) -2-phenylethine was obtained. (Yield 75%).

In the same manner as in Example 2, 5- (2-phenylethynyl) isophthalic acid dipotassium salt, 5- (2-phenylethynyl) isophthalic acid and 5- (2-phenylethynyl) isophthalic acid dichloride Appearance, melting point and ¹ H-NMR, ¹³ C-NMR, IR, MS, element of 5- (2-phenylethynyl) isophthalic acid and 5- (2-phenylethynyl) isophthalic acid dichloride The spectral data of the analysis all showed that the same compound was obtained in accordance with Example 2.

(Example 5)

[Production of 5- (4-nitrophenoxy) isophthalic acid dimethyl]

133.24 g (0.63 mol) of 5-hydroxy isophthalic acid and 107.33 g (0.76 mol) of 4-fluoro nitrobenzene in a 2 L four-necked flask equipped with a thermometer, stirrer and Dean Stack distillation, N, N-dimethyl formamide 760 m 1 and 190 m 1 of toluene were added thereto, and the byproduct water was stirred at 165 ° C. for 4 hours while azeotropically removing the byproduct water. After cooling, the reaction solution was poured into 3 L of ion-exchanged water to precipitate the product. The precipitate was taken, washed with ion-exchanged water and ethanol, and the resulting pale yellow solid was dried under reduced pressure at 50 ° C. for 1 day to obtain 142.01 g of the product ( Yield 68%).

[Preparation of 5- (4-Aminophenoxy) isophthalic Acid Dimethyl]

Into a 1 L Nasu flask, 66.24 g (0.2 mol) of 5- (4-nitrophenoxy) isophthalic acid dimethyl, 6.39 g of 10% by weight of palladium-activated carbon, 440 m1 of tetrahydrofuran, 220 m1 of ethanol were added thereto. The reaction mixture was stirred for 24 hours. The reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. To this was added hexane, and the precipitate was taken, and the white solid obtained was dried under reduced pressure at 50 ° C for 1 day to obtain 55.96 g of a product. (Yield 93%).

[Production of 5- (4-iodinephenoxy) isophthalic acid dimethyl]

In a 1 L four-necked flask equipped with a thermometer, agitator, and dropping lot, 450 m 1 of ion-exchanged water, 75 m 1 of concentrated sulfuric acid, and 45.20 g (0.15 mol) of 5- (4-aminophenoxy) isophthalic acid dimethyl obtained above were stirred. . The flask was cooled to 5 ° C. or lower, and 12.42 g (0.18 mol) of sodium nitrite was added dropwise to 25 ml of ion-exchanged water for 20 minutes, and stirred at 5 ° C. or lower for 40 minutes to obtain an aqueous diazonium salt solution. To this solution, 27.39 g (0.165 mol) of potassium iodide was dissolved in 33 m1 of ion-exchanged water. Then, the mixture was stirred at 5 ° C. or lower for 1 hour and at room temperature for 1 hour. The precipitate was taken up, dissolved in 300m1 of ethyl acetate, and then washed twice with 200 ml of 10% by weight aqueous sodium hydrogen sulfite solution and twice with 200 ml of ion-exchanged water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and a small amount of hexane was added. A brown crude product was precipitated. The product was extracted with hexane using a Soxhlet extractor, recrystallized with methanol after removal of the solvent to give a pale yellow solid. The separated solid was dried under reduced pressure at 50 ° C. for 1 day to obtain 25.40 g of a product (yield 41%).

[Preparation of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dimethyl]

In a 500m1 four-necked flask equipped with a thermometer, a cooling tube and a nitrogen inlet tube, 24.73 g (0.06 mol) of 5- (4-iodinephenoxy) isophthalate obtained above, 0.79 g (0.003 mol) of triphenyl phosphine ), 0.23 g (0.0012 mol) of copper iodide, 6.74 g (0.066 mo1) of ethynylbenzene, 72 ml of dehydrated triethylamine, 38 m1 of dehydrated pyridine, 0.25 g of dichloro bis (triphenylphosphine) palladium, and nitrogen. The mixture was heated to reflux at 105 DEG C for 1 hour while flowing. Triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. 200m1 of water and 5m1 of hydrochloric acid were injected into this, and the precipitated solid substance was taken out. Furthermore, it washed with 500m <1> of water. The solid was dried under reduced pressure at 50 degreeC for 1 day, and the product 17.39g was obtained (yield 75%).

[Preparation of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dipotassium salt]

450 ml of n-butanol and 47.53 g (0.32 mole) of potassium hydroxide (85% by weight) were added to a 1 L Nasu flask, and the mixture was heated to reflux and dissolved. 5- (4- (2-phenylethynyl) obtained as described above. Phenoxy) 15.46 g (0.04 mol) of dimethyl isophthalic acid were added and heated to reflux for 30 minutes. This was cooled in an ice bath to precipitate precipitated crystals. The crystals were washed twice with 200m &lt; 1 &gt; of isopropanol, and then dried under reduced pressure at 50 deg. C to obtain 16.86 g of a product (yield 97%).

[Preparation of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid from 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dipotassium salt]

8.69 g (0.02 mol) of 5- (4- (2-phenylethynyl) phenoxy isophthalic acid dipotassium salt obtained above was dissolved in 40 ml of ion-exchanged water and filtered with 5C filter paper to remove insoluble matters. Hydrochloric acid was added to the solution with stirring until the pH became 1. The precipitated solid was taken, and then washed with ion-exchanged water and filtered twice. The obtained solid was dried under reduced pressure at 50 ° C and the product was 6.88 g. Was obtained (yield 96%).

[Preparation of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride from 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dipotassium salt]

In a 500m1 four-necked flask equipped with a thermometer and a cooling tube, 15.2 g (0.035 mol) of 2-potassium isophthalic acid salt, 90m1 of chloroform was added. 62.46 g (0.525 mol) of thionyl chloride was dripped at 5 degrees C or less for 15 minutes. Then, 0.7 m1 of dimethylformamide and 0.7 g of hydroquinone were added and stirred at 45-50 degreeC for 3 hours. After cooling, the crystals were separated by filtration, and the crystals were washed with 50 m1 of chloroform. The filtrate and the washing liquid were combined, concentrated under reduced pressure at 40 ° C or lower, and the obtained residue was extracted and recrystallized with n-hexane. Drying under reduced pressure afforded 3.44 g of product (yield 25%).

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[Preparation of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride from 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid]

In a 500m1 four-necked flask equipped with a thermometer and a cooling tube for cooling, 12.54 g (0.035 mol) of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid, 100 ml of 1,2-dichloroethane, 9.16 g (0.077 mole) of thionyl chloride and 8.0 mg (0.00035 mole) of benzyl triethylammonium chloride were added thereto, and the mixture was heated to reflux for 3 hours. The solution was filtered under heat (heating), the filtrate was concentrated under reduced pressure, and recrystallized by adding hexane. . The obtained solid was dried under reduced pressure and 6.33 g of product was obtained (yield 46%).

The spectral data of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid and 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride obtained are shown as follows. Supports that the obtained compound is the target product.

[5- (4- (2-phenylethynyl) phenoxy) isophthalic acid (C ₂₂ H ₁₄ O ₅ )]

Appearance: white solid

Melting point: Not observed below 320 ° C (DSC, 10 ° C / min)

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 13.47 (br), 8.25 (s, 1H), 7.71 (s, 2H), 7.61 (d, 2H), 7.53 (m, 2H), 7.40 ( m, 3H) ， 7.13 (d, 2H)

¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 166.12, 156.96, 156.29, 133.79, 133.54, 131.54, 128.95, 125.29, 123.11, 122.51, 119.82, 118.45, 89.37, 88.90

IR (KBr, cm ^-1 ): 3424, 2826, 2568, 1713, 1589, 1504, 1466, 1418, 1322, 1284, 1241, 1206, 1165, 1102, 197, 846, 758, 691

MS (FD) (m / z): 358.2 (M ⁺ )

Elemental Analysis:

Theoretical C: 73.74% H: 3.94%                 

Found C: 73.31% H: 3.84%

[5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride (C ₂₂ H ₁₂ O ₃ Cl ₂ )]

Appearance: Light Yellow Solid

Melting Point: 130 ℃ (DSC ， 10 ℃ / min)

¹ H-NMR (400MHz, CDC1 ₃ ): δ8.56 (s, 1H), 7.98 (s, 2H), 7.59 (d, 2H), 7.52 (m, 2H), 7.35 (m, 3H), 7.04 ( d, 2H)

¹³ C-NMR (100 MHz, CDCl ₃ ): δ 166.65, 158.27, 154.82, 135.78, 133.77, 131.54, 128.41, 128.35, 127.90, 125.96, 122.87, 120.40, 119.54, 89.84, 88.14

IR (KBr, cm ^-1 ): 3446,1754,1588,1506,1443,1202,1218,1145,991,846,824,764,737,694,683

MS (FD) (m / z): 394.2 (M ⁺ )

Elemental Analysis:

Theoretical C: 67.20% H: 3.08% C1: 17.52%

Found C: 66.65% H: 2.99% Cl: 17.99%

(Example 6)

[Production of 5- (4-hydroxyphenoxy) isophthalic acid dimethyl]                 

45 L 20-dimethyl dimethyl 5- (4-aminophenoxy) isophthalate obtained in the same manner as in Example 5 in a 1 L four-necked flask equipped with a thermometer, stirrer, and dropping lot. The flask was cooled to 5 ° C. or lower, and 12.42 g (0.18 mol) of sodium nitrite was added dropwise to 25 ml of distilled water over 20 minutes, and stirred at 40 ° C. or lower for 40 minutes and stirred at 100 ° C. for 2 hours. It was. The precipitate was taken, treated with activated carbon in methanol, and recrystallized. The filtered solid was dried under reduced pressure at 50 ° C. for 1 day to obtain 23.58 g of a product (yield 52%).

[Preparation of 5- (4-trifluoromethane sulfonyloxyphenoxy) isophthalic acid dimethyl]

In a 1 L four-necked flask equipped with a thermometer, a zigzag cooling tube, a calcium chloride tube and a stirrer, 21.26 g (0.07 mol) of 5- (4-hydroxyphenoxy) isophthalate dimethyl obtained above, 300 m1 of dehydrated toluene and dehydrated pyridine 16.61 g (0.21 mol) was added and cooled to 30 DEG C while stirring. Here, 39.50 g (0.14 mol) of trifluoromethane sulfonic anhydride was slowly added dropwise, taking care not to increase the temperature to -25 DEG C or higher. The reaction temperature was raised to 0 ° C. for 1 hour and the reaction temperature was increased to room temperature for 5 hours. The obtained reaction mixture was poured into 400 m 1 of ice water and separated into an aqueous layer and an organic layer. Subsequently, the aqueous layer was extracted twice with 100 m 1 of toluene. The organic layer was washed twice with 300 ml of water, dried over anhydrous magnesium sulfate, distilled off the solvent under reduced pressure, and recrystallized with hexane. It dried under reduced pressure at 1 degreeC for 1 day, and obtained 26.14 g of products (yield 86%).

[Production of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dimethyl]                 

In Example 5, 24.73 g (0.06 mol) of 5- (4-iodinephenoxy) isophthalic acid dimethyl 26.06 g (0.06) of 5- (4-trifluoromethane sulfonyloxyphenoxy) isophthalic acid obtained above Mole) was obtained in the same manner as in Example 5 to obtain 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dimethyl.

In the same manner as in Example 5, 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dipotassium salt, 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid, 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride was obtained. Appearance, melting point and ¹ H-NMR, ¹³ C- of 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid and 5- (4- (2-phenylethynyl) phenoxy) isophthalic acid dichloride The spectral data of NMR, IR, MS, and elemental analysis were all in agreement with Example 5 to show that the same compound was obtained.

According to the present invention, an aromatic carboxylic acid and an acid halide derivative thereof useful as a raw material of a polymer compound, especially a condensed polymer compound having excellent heat resistance, and the like can be easily provided.

Claims (11)

General formula (1)

[Wherein A is the following equation -C ≡CR ¹ ... (a) or

(Wherein R ¹ is an alkyl group selected from the group consisting of a hydrogen atom, an ethyl group, a propyl group and a butyl group or an aromatic group selected from the group consisting of a phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group, and R ² is Alkyl group selected from the group consisting of ethyl group, propyl group and butyl group or aromatic group selected from the group consisting of phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group.). Aromatic carboxylic acid, characterized by having a structure represented by. General formula (2)

[Wherein A is the following equation -C ≡CR ¹ ... (a) or

(Wherein R ¹ is an alkyl group selected from the group consisting of a hydrogen atom, an ethyl group, a propyl group and a butyl group or an aromatic group selected from the group consisting of a phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group, and R ² is An alkyl group selected from the group consisting of an ethyl group, a propyl group and a butyl group or an aromatic group selected from the group consisting of a phenyl group, a naphthyl group, an anthryl group, a quinolyl group and a quinoxalyl group.), X represents a halogen atom .] An acid halide derivative of an aromatic carboxylic acid having a structure represented by. The method of claim 2, An acid halide derivative of an aromatic carboxylic acid, wherein in formula (2), X is a chlorine atom. General formula (3)

[Wherein D represents a leaving group and R represents a methyl group] Compound represented by and general formula (4) HC ≡C-E ... (4) [Wherein E is an aromatic group selected from the group consisting of an alkyl group selected from the group consisting of trimethylsilyl group, hydroxypropyl group, ethyl group, propyl group and butyl group or phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group Represents a group.] Reacting the compound represented by the following general formula (5),

[Wherein R and E have the same meanings as above] After obtaining the compound represented by the following formula (6) by treating in the presence of an alkali metal hydroxide

[Wherein R ¹ is an alkyl group selected from the group consisting of hydrogen atom, ethyl group, propyl group and butyl group or aromatic group selected from the group consisting of phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group, M is alkali A metal is represented.] General formula (1-1), characterized in that the compound represented by the above is produced and subsequently acid treated.

[Wherein, R ¹ is as defined above.] Method for producing an aromatic carboxylic acid represented by. The method of claim 4, wherein In the reaction of a compound represented by the general formula (3) with a compound represented by the general formula (4), a transition metal catalyst is used. General formula (7)

[Wherein D represents a leaving group and R represents a methyl group] Compound represented by general formula (8) HC ≡CR ² ... (8) [Wherein R ² represents an alkyl group selected from the group consisting of ethyl group, propyl group and butyl group or an aromatic group selected from the group consisting of phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group.] By reacting the compound represented by the formula (9)

[Wherein R and R ² are the same as defined above.] After obtaining a compound represented by the following treatment in the presence of an alkali metal hydroxide, a general formula (10)

[Wherein M represents an alkali metal and R ² is as defined above.] General formula (1-2), characterized in that the compound represented by

[Wherein, R ² is as defined above.] Method for producing an aromatic carboxylic acid represented by. The method of claim 6, The manufacturing method of the aromatic carboxylic acid using a transition metal catalyst in reaction of the compound represented by General formula (7), and the compound represented by General formula (8). General formula (1-1)

[Wherein R ¹ represents an alkyl group selected from the group consisting of a hydrogen atom, an ethyl group, a propyl group and a butyl group or an aromatic group selected from the group consisting of a phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group.] Compound represented by or General formula (6)

[Wherein M represents an alkali metal and R ¹ is as defined above.] General formula (2-1) characterized by treating the compound represented by the halogenating agent

[Wherein X represents a halogen atom and R ¹ is as defined above.] Method for producing an acid halide derivative of aromatic carboxylic acid represented by. The method of claim 8, A process for producing an acid halide derivative of an aromatic carboxylic acid wherein the halogenating agent is a chlorinating agent and X is a chlorine atom in the general formula (2-1). General formula (1-2)

[Wherein R ² represents an alkyl group selected from the group consisting of an ethyl group, a propyl group and a butyl group or an aromatic group selected from the group consisting of a phenyl group, naphthyl group, anthryl group, quinolyl group and quinoxalyl group.] Compound represented by or General formula (10)

[Wherein M represents an alkali metal and R ² is as defined above.] Formula (2-2), characterized in that the compound represented by the treatment with a halogenating agent

[Wherein X represents a halogen atom and R ² is as defined above.] Method for producing an acid halide derivative of aromatic carboxylic acid represented by. The method of claim 10, A process for producing an acid halide derivative of an aromatic carboxylic acid wherein the halogenating agent is a chlorinating agent and X is a chlorine atom in the general formula (2-2).